Process of treating liquids



Patented Mar. 8, 1927.

carried on by the softenin or treating UN'lTE D S TA TE-S. PATENT oF WILSON EVANS, OF CHICAGO, ILLINOIS,

POBATION, OI. CHICAGO,

1,520,333 ics.

n'ssrenoa r0 Annamaria; was con- ILLINOIS, a coaromrron or rumors.

PROCESS TREATING LIQUIDS.

No Drawing. Application filed Kay 28,

My invention relates to improvements in processes of treating water and is prlmarlly adapted for the cold treatment of water in softening plants adapted to prepare 1t for commercial purposes such as use in bollers, laundries, fruit cannin plants, dye-houses, chemical processes, or or domestic uses. I propose to use injconnection with any ord1-- nary water softening or treat ng mixture, a reagent which will expedite and cause to progress nearer to completion the process mixture and to some extent by the additional reagent itself, and which coagulate or flocculate the resultant precipitate so as to carry down and settle out such precipitate and any other matter which may be m suspension, thus rendering settling or filtration easier and more ra 1d and positive. I propose to mix this additional reagent or catalyst with the water after the introduction of the other renting elements which are used in connection with it and of course in this case it becomesnecessary to provide separate means for in troducingthe various reagents at different times. y

The rea ent or catalyst which I propose to use is sogium aluminate which 1s or example present in the liquid obtained by digesting either the rawmineral bauxite or aluminum hydroxide (commerciallyreferred to as bauxite ore concentrates) with suitable portions of soda ash and lime or with caustic soda, and, in case the raw bauxite is used or the digestion accomplished with lime and soda"-ash,-if desired, filtering, and under some circumstances, concentrating the fil-' trate to any desired and feasible point. The

-active ingredient in the resulting liquid in the process I propose, is in any case its sodlum alummate content, and for convemence this liquid will hereafter be referred-to as sodium aluminate solution. It should be particularly noted, however, that an excess of caustic soda in 'the'sodium aluminate solution, either added as suchor deried from lime and soda ash in digesting, is desirable inorder to prevent the raid precipitation of faluminumhydrat'e from the liquid. Other '50 in Fredients resent in' -tlie sodium aluminate ution', suc as organic matter and soda ash, are thereonly due 'toprocess -of manufacture followed. The viscosity of the sodium Illuminate-solution increases as its contents the amount of water process, or by evaporation of the resultant 1925. Serial m. 33,055.

of sodium aluminate and'caustic soda is increased and it has been found desirable to limit the content of sodium aluminate in the commercial solution to about thirty-five percent with about five percent excess caustic soda. although it is possible to produce in exactly the same manner by sim 1y reducing used in t e digesting liquid, a sodium aluminate solution containmg a considerably greater percentage of sodium aluminate, but such a solution, particularly when cold, becomes so viscous as to make its handling difiicult for commercial use.

For purposes of illustration, the following 1s a statement of a satisfactory batch of my material 205 lbs commercial caustic soda solutron, gravity approx. 1.53; 140 lbs. commerc1al bauxlte ore concentrates, 64% alumina (A1 0 7 6 lbs water; total 421 lbs. sodium valuminat-e solution, gravit approx. 1.52, consodlum a uminate and 7.6% v

taining 34.30% excess caustic soda. 1

My process is preferably carried on in connectlon with water softening or treating by the lime, soda ash process. The purpose of such treatment independentof my invention is to remove from the water the dissolved calcium and magnesium salts present largely in the form of bi-carbonates, carbonates and sulphates. The lime is used to convert the soluble calcium, bi-carbonate into the corresponding insoluble carbonateand also to" convert the soluble magnesium bicarbonate into the corresponding partially soluble magnesium carbonate which latter is reacted upon by a further'amount of lime to form the insoluble ma esium hydroxide, such action being expe itedand carried further toward completion by my treatment. The soda ash converts the calcium sulphate into the corresponding insoluble carbonate and converts the magnesium sulphate into /the partially soluble magnesium carbonate which is in turn, the treatment and converted into their!- soluble"-'-ma(g'nesium hydroxide, such action being expe i completion by my treatment. Ex rience shows that, particularly when water 1s treatacted upon my the lime used in.

tedand carried further toward 5 ed cold with lime and soda ash only, the re actions above indicated, especiallymso. far as '1 and only to a the formation of the insoluble magnesium hydroxide is concerned, progresses very slowpartial extent, and in order to secure reasonably complete elimination of the dissolved calcium and magnesium salts it is necessary to employ a considerable excess amount of soda ash andlime. As an illustration of this action the following testmade on a sample of hard water may be cited.-

The untreated water showed hardness by the conventional soap test to be 16.5 grains per gallon on the basis of calcium carbonate with a total alkalinity determined by methyl orange titration of 13.3 grains per gallon also expressed as calcium carbonate.

The following tabulation shows tests on this water treated with proper amounts of lime and sodaash, the figures showing results of the tests being expressed under the,

headings H, A and G, H referring to hardness by soap tests, A referring to alkalinity by methyl orange titration, and G referring to twice the phenolpthalein titration, the term C being used to represent causticity as this is popularly although incorrectly referred to as such. Tests referred to are as follows:

In the above test the excess reagents are indicated by the difierence between the H and A values, and the difference between the A and C values represents that portion of the excess which is present as caustic soda or if the difference between A and C is greater than between H and A then the tot-a1 excess is the difference between A and C, of which the AI-I difference represents caustic soda and the remainder free lime existing in the form of calcium hydrate. Not only do the reactions as outlined in cold water progress slowly and incompletely but the precipitates formed when lime and soda ash only are used for treatment are very fine and settle slowly and when filtration is used, water so treated filters with difiiculty, resulting sometimes in cloudy effluent especially at high rates of filtration. Moreover, even when the visible precipitates have been settled or filtered and the water is crystal clear, there is an after-reaction which results in the very gradual though long, continued formation of precipitates, which are deposited on the ains ofsand or silica used as a filtering medlum, or on the pipes through which the water flows, causing the individual grains to grow, or the pipes to be gradually clogged. If the crystal clear water which has been treatedby the lime, soda ash process is introduced into a boiler or otherwise heated, the after-reaction is greatly speeded up with the formation of further precipitates in relatively large quantities, causing foaming and scale formation, and this difiiculty is increased, if in the effort to insure complete reaction an increased amount of the softening reagents has been used.

It is to avoid the difiiculties above referred to that Ihave developed my process. The manner in which this is accomplished may be well illustrated by quoting results of parallel tests made on the same water referred to above. In this case there was used for its treatment lime, soda ash, and sodium aluminate solution in proper quantities, the tests on the treated water being as follows:

Time alter treatment. H. A. C.

20 minutes 4. 3 4. 7 5.0 1 hour, 30 minutes 3. 3 4. 4 4. 2 2 hours, 30 minutes 3. 4 4. 2 4. 4

It will be noted from these tests that the excess reagents as indicated by the differences above outlined have been to a large extent eliminated. Many other tests have been made showing complete elimination of excess reagents with water carried down to a lower point in hardness but these particular tests are quoted as they were made using a quantity of sodium aluminate solution considered feasible for commercial use, and were being at the time duplicated in a softening plant treating 600,000 gallons of water for 24 hours. In the case of all tests the results of which are quoted above both when using the lime and soda ash alone and when using lime, soda ash and sodium aluminate solution, the water was initially treated at a temperature of 46 F. and did not exceed that temperature until tests as above quoted were made.

Experience shows that at temperatures as low as 34 F. equally as good results can be obtained with the sodium alurhi'nate solution, while the results obtained without it become increasingly worse as the temperature falls. Due to thelower hardness obtained andthe smaller excess of reagents in the treated water, this water-was rendered much more suitable for the purposes for which it'was treated. The after-reaction above referred to is done away with to the extent that excess treatment is eliminated, and further the precipitates are much larger and are coagulated so as to settle rapidly and also carry down with them at a rapid rate any foreign matter which may be suspended in the water.

My process is carried out by introducing into the water which has previously been mixed or treated with lime and soda ash or with-either alone a suitable quantity of sodium aluminate solution. When this is done rapid precipitation and coagulation takes place and the precipitate settles down in a flocculent form carrying with it as above indicated the organic or other matter which may be in suspension in the water. water and the precipitates are then separated in any suitable wayasby drawin off the clear, super-natant water, and if desired, by filtering, although this is not ordinarily necessary with my process on account of the I greatly improved settling secured by it.

he resultant clarified, purified, softened water will then be fed directly into the boiler and can be heated without bringing down any appreciable amount of 'further re'cipitate, or it may be used in the manuacture of artificial me where, owing to the absence of the salts otherwise present, better, less brittle and clearer ice is formed, or

this watermay be satisfactorily .used for the other purposes for which eluding domestic uses.

With reference to the claims it must be em hasized that b the use of the term sod ium aluminate do not wish-to be limit is intended inited to chemically pure sodium aluminate,

or of any other softening compounds used in the water. It may be used in such quantities as not at all to be .suflicient by itself for water softening. It may be used in such quantities that the totalquantity of it with other compounds would, if the activity of the sodium aluminate were only that norv mally to be expected, be quite inadequate for satisfactory water softening; but when combined with the other water softening compounds it has an expediting of speeding up effect, reinforcing and furthering the action of the, rdinary water treating compounds, and resulting in an increased preciygictlahtion and coagulation.

en water containing calcium and magnesium salts or water containing either a calcium or a magnesium salt is treated sodium aluminate and any standard water treating compound, either calcium or magnesium aluminates or both are formed. Either of these substances are very effective as a coagulant and their resence in the water results in the quick occulation of the precipitates brought down by the water The softening compound. The formation of the 7 calcium and ma esiumf aluminates is illustrated by the fo owing formulae:

( Magnesium sulphate plus sodium aluminate==maguesium aluminate plus sodium sulphate.)

(Magnesium bicarbonate plus sodium aluminutc magnesium aluminate plus sodium carbonate plus carbon dioxide plus water.)

MgCl +NA Al O =M A1,o,+2Nac1 (Magnesium chloride plus sodium aluminate magnesium aluminate plus sodium chloride.)

. CaSO,+Na,Al O =CaAl O l-Na SO (Calcium sulphate plussodium a1u|ninate=1culcium aluminate plus sodium sulphate.)

(Calcium bicarbonate plus sodium aluminate-=calcium aluminate lus sodium carbonate plus carbon dioxide plus waters? CaCI +Na-,AI O =CaAl,O,+2NaCl I (Calcium chloride plus sodium aluminates-calcium alumi- A nate plus sodium chloride.)

The coagulants that is to sa calcium or magnesium aluminates, forme by the use of sodium aluminate differ widely not only in their composition but also in from those coagulants formed by the use of other aluminum compounds for example aluminum sulphate or alum. When alumi-' their effect.

whereas calcium and magnesium aluminates are insoluble thru a wide range of hydrogen ion concentrations including the range in which most commercial water softening takes place. Thisisparticularlytrueofmagnesium aluminate and where ma esium is present in the waterbeing treated this com ound is.

instantly formed due. to the fun amental a.

law of chemical reaction to the effect "that in a mixture of compounds which ma react one u on another the most insolub e compoun will be formed. Therefore by the use of sodium aluminate in connection with any magnesium carrying water, there is obtained a coagulant eifective through an extremely wide range of h drogen ion con-. centration the presence 0 which results in guick settling of the precipitants brought own by the water softening com ound and due to breaking down-the semi-co loidal and complex compounds contained in the water. The g'eaction with the water softening compound is carried to completion rapidly so that there is no after-reaction progressing in the treated water, which after-reaction would otherwise continue fora considerable period of time resulting in the incrustation of pipe lines through which the water is transmitted or vessels in which it is stored.

For some purposes and with some waters,

narily producing a water of as low hardness as where lime soda ash and sodium aluminate are used, still produces a satisfactory result in that the sodium aluminate insures the practical completion of the lime reactions. If lime alone or, as in some cases, lime and aluminum sulphate or alum is used the reactions do .not progress as rapidly or as near to absolute completion as with the lime and sodium aluminate nor is such rapid settling obtained, and the difiiculties resulting from after-reaction are present.

I claim: 1 1. The process of treating liquids which consists in mixing in solution lime, soda ash, mixing-the resultant product with the liquid to be treated, and then adding sodium aluminate and separating the resultant precipitates from the liquid.

2. The process of treating liquids which consists in mixing in an aqueous solution lime and soda ash, then mixing the resultant product with the liquid to be treated, and

then adding sodium aluminate and separat- 'consists'in adding thereto a softening compound adapted to react 0n the water to recipitate out insoluble salts and then ad ing to the water thus treated sodium aluminate and separating the water and the precipitates thus formed.

4. The process of treating liquids which consists in mixing lime with the liquid and then separately adding sodium aluminate thereto and separating the resultant precipitates from the liquid.

5. The process of treating liquids which consists in mixing with the liquid an aqueous solution of lime, then addin aluminate to the treated liquid an separating the resultant precipitates from the liquid. I

(3. The process of treating liquids which consists in making up a mixture of lime and soda ash, adding the mixture to the liquid sodium to be treated, then separately adding sodium I aluminate and separating the resultant precipitates from the liquid.

7. The process of softening water which consists in adding thereto lime and soda ash and then separately adding thereto sodium aluminate in such proportions and quantities that the amount of sodium aluminate is insuflicient to effect any adequate softening by itself but is sufficient to expedite and insure adequate softening by the other ingredients.

Signed at Chicago, county of Cook and State of Illinois, this 8th day of May, 1925.

' WILSON EVANS. 

